US9206353B2 - Metal nano particles doped with silicate luminescent materials and preparation methods thereof - Google Patents

Metal nano particles doped with silicate luminescent materials and preparation methods thereof Download PDF

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US9206353B2
US9206353B2 US13/812,908 US201013812908A US9206353B2 US 9206353 B2 US9206353 B2 US 9206353B2 US 201013812908 A US201013812908 A US 201013812908A US 9206353 B2 US9206353 B2 US 9206353B2
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US20130126785A1 (en
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Mingjie Zhou
Rong Wang
Chaopu Shi
Wenbo Ma
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Oceans King Lighting Science and Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/87—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing platina group metals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
    • C09K11/77342—Silicates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
    • C09K11/7734—Aluminates

Definitions

  • the present invention relates to a luminescent material and the preparation method thereof, and particularly, to a metal nanoparticles doped silicate luminescent material and the preparation method thereof.
  • white light LED As a new type of solid light source, white light LED has the advantages of energy-saving, environmental protection, long life, small size and the like, thus it has great application prospects in the fields of lighting and display.
  • white light LEDs There are two types of white light LEDs: the first one is consisted of three LEDs: red, blue, and green; the second one is composed of LED chip and the phosphor powder coated thereon.
  • the second type is now widely employed the manufacturing method of the white light LED composed of a blue light LED chip and a yellow phosphor powder which may be excited by blue light is simple, the luminous efficiency of the product is high, thereby it is the preferred product to implementation of white light LED, wherein the yellow phosphor powder is mainly composed of YAG fluorescent powder.
  • the silicate phosphor powder is also a good yellow phosphor powder. Compared to the YAG phosphor powder, the excitation spectrum of the silicate phosphor powder is wider, and has a better color purity, but this phosphor powder has the problem of low luminous efficiency. However, further improving the luminescent properties of the material is the target of the researchers.
  • the technical problem to be dissolved by the present invention is to provide a metal nanoparticles doped silicate luminescent material and the preparation method thereof.
  • a metal nanoparticles doped silicate luminescent material is provided, the general formula thereof is (Sr 1-x-y A x Eu y ) 3 SiO 5 :D z @M n , wherein A is one or two selected from alkaline earth metal elements, D is F or Cl, @ represents coating, M is metal nanoparticle, and the metal is one or two selected from the group consisting of Ag, Au, Pt, Pd or Cu metal nanoparticles, the value of x is: 0 ⁇ x ⁇ 0.5, the value of y is: 0.001 ⁇ y ⁇ 0.15, the value of z is: 0 ⁇ z ⁇ 0.5, n is the molar ratio of the metal nanoparticles to the silicon elements, and the value of n is: 0 ⁇ n ⁇ 0.01.
  • the A is one or more selected from the group consisting of Ba, Ca, Mg and Zn.
  • the value of x is: 0.05 ⁇ x ⁇ 0.3; the value of y is: 0.01 ⁇ y ⁇ 0.1, the value of z is: 0.01 ⁇ z ⁇ 0.13; the value of n is: 1 ⁇ 10 ⁇ 4 ⁇ n ⁇ 5 ⁇ 10 ⁇ 3 .
  • the preparation method of a metal nanoparticles doped silicate luminescent material comprises:
  • step 1 a metal salt solution, an additive and a reductant together are mixed together and react with each other to obtain a metal nanoparticle colloid, wherein the metal is one or two selected from the group consisting of Ag, Au, Pt, Pd, and Cu;
  • step 2 the metal nanoparticle colloid is subjected to surface treatment by adding a solution containing a surface treating agent thereto, then an absolute ethanol, a deionized water, an aqueous ammonia, and a tetraethyl orthosilicate are added to the solution to prepare a coating SiO 2 nanospheres, and the acidity of the solution is adjusted to pH5;
  • step 3 a nitrate solution of Sr, A, and Eu, as well as a nitric acid solution or aqueous solution of SrD 2 or AD 2 are added into the final solution obtained in step 2 in accordance with the stoichiometric ratio of the corresponding elements in the general formula (Sr 1-x-y A x Eu y ) 3 SiO 5 : D z , @M n wherein A is one selected from alkaline earth metal elements, D is F or Cl, the value of x is: 0 ⁇ x ⁇ 0.5, the value of y is: 0.001 ⁇ y ⁇ 0.15, the value of z is: 0 ⁇ z ⁇ 0.5, then a precipitating agent is added, after stirring the precipitate is dried to obtain the precursor;
  • step 4 the precursor is subjected to heat treatment and reduction treatment, and then it is cooled to give the metal nanoparticles doped silicate luminescent material.
  • the additives are one or more selected from the group consisting polyvinylpyrrolidone, sodium citrate, cetyl trimethyl ammonium bromide, sodium dodecyl sulfate and sodium dodecyl sulfonate, and the additive is added in such an amount that the content thereof in the final metal nanoparticle colloid is in the range of 1 ⁇ 10 ⁇ 4 g/ml to 5 ⁇ 10 ⁇ 2 g/ml.
  • the reductant is one or more selected from the group consisting of hydrazine hydrate, ascorbic acid, sodium citrate, and sodium borohydride, and the reductant is added in such an amount that the molar ratio of the reductant to the metal ions is in the range of 3.6:1 to 18:1.
  • the surface treating agent is polyvinyl pyrrolidone
  • the solvent is water
  • the concentration of the surface treating agent is in the range of 0.005 to 0.1 g/ml.
  • the precipitating agent in step 3 is ammonium carbonate, and the ammonium carbonate is in excess of 25% in the amount of substance in the solution of step 3 .
  • the heat treatment in step 4 is that the precursor being placed in a muffle furnace at 600° C. to 1000° C. for 2 to 10 hours.
  • the reduction treatment is that the heat treated precursor being reduced at 1300° C. to 1600° C. for 1 to 8 hours in a reducing atmosphere, and the reducing atmosphere is one or more selected from the group consisting of a mixed gas of nitrogen and hydrogen, carbon monoxide, and pure hydrogen.
  • the core-shell structure of the luminescent material is formed by coating metal particles, which improves the internal quantum efficiency of the luminescent material, and the added metal nanoparticles enhances its luminous intensity, furthermore the luminescent material has good stability, and has a spherical profile, and the size, profile thereof is controllable, the spherical profile has a higher bulk density, which facilitates the process of coating screen and improves the display effect of the coated screen; additionally, the present method employs the process of precipitation, which lowers the temperature of the synthesis reaction, and the process for preparation is simple, low equipment requirements, pollution-free, easy to control, thus has broad prospects for production applications.
  • FIG. 1 is a flow chart of preparation method of the a metal nanoparticles doped silicate luminescent material of the present invention.
  • FIG. 2 shows the comparison spectrum at 460 nm excitation of the luminescent material prepared in Example 4 according to the present invention, wherein the curve 1 is the emission spectrum of the non Ag metal nanoparticles coated luminescent material of (Sr 0.97 EU 0.03 ) 3 SiO 5 :F 0.15 , and the curve 2 is the emission spectrum of the Ag metal nanoparticles coated luminescent material of (Sr 0.97 EU 0.03 ) 3 SiO 5 :F 0.15 @Ag 2.5 ⁇ 10 ⁇ 4 .
  • the present invention provides a metal nanoparticles doped silicate luminescent material, the general formula thereof is:(Sr 1-x-y A x Eu y ) 3 SiO 5 :D z @M n , wherein A is one or two selected from alkaline earth metal elements, D is F or Cl, @ represents coating, M is metal nanoparticle, and the metal is one or two selected from the group consisting of Ag, Au, Pt, Pd and Cu metal nanoparticles, the value of x is:0 ⁇ x ⁇ 0.5, the value of y is: 0.001 ⁇ y ⁇ 0.15, the value of z is: 0 ⁇ z ⁇ 0.5, n is the molar ratio of the metal nanoparticles to the silicon elements, and the value of n is: 0 ⁇ n ⁇ 0.01.
  • the coating means that the metal nanoparticle being as the core, and the (Sr 1-x-y A x Eu y ) 3 SiO 5 :D z phosphor powder being as the shell.
  • the A is one or more selected from the group consisting of Ba, Ca, Mg and Zn.
  • the value of x is: 0.05 ⁇ x ⁇ 0.3; the value of y is: 0.01 ⁇ y ⁇ 0.1, the value of z is: 0.01 ⁇ z ⁇ 0.13; the value of n is: 1 ⁇ 10 ⁇ 4 ⁇ n ⁇ 5 ⁇ 10 ⁇ 3 .
  • FIG. 1 shows the flow of the preparation method of the a metal nanoparticles doped silicate luminescent material of the present invention, which comprises:
  • step S 01 a metal salt solution, an additive and a reductant are mixed together and react with each other to give a metal nanoparticle colloid, wherein the metal is one or two selected from the group consisting of Ag, Au, Pt, Pd, and Cu;
  • step S 02 the metal nanoparticle colloid is subjected to surface treatment by adding a solution containing a surface treating agent thereto, then an absolute ethanol, a deionized water, an aqueous ammonia, and tetraethyl orthosilicate are added to the solution to prepare a coating SiO 2 nanospheres, and the acidity of the resulted solution is adjusted to pH 5;
  • step S 03 a nitrate solution of Sr, A, and Eu, as well as a nitric acid solution or aqueous solution of SrD 2 or AD 2 are added into the final solution obtained in step S 02 in accordance with the stoichiometric ratio of the corresponding elements in the general formula of (Sr 1-x-y A x Eu y ) 3 SiO 5 :D z , @M n wherein A is one selected from alkaline earth metal elements, D is F or Cl, the value of x is: 0 ⁇ x ⁇ 0.5, the value of y is: 0.001 ⁇ y ⁇ 0.15, the value of z is: 0 ⁇ z ⁇ 0.5, then a precipitating agent is added, after stirring the precipitate is dried to obtain the precursor;
  • step S 04 the precursor is subjected to heat treatment and reduction treatment, then it is cooled to give the metal nanoparticles doped silicate luminescent material.
  • the additive is one or more selected from the group consisting of polyvinylpyrrolidone, sodium citrate, cetyl trimethyl ammonium bromide, sodium dodecyl sulfate and sodium dodecyl sulfonate, and the additive is added in such an amount that the content thereof in the final metal nanoparticle colloid is in the range of 1 ⁇ 10 ⁇ 4 g/ml to 5 ⁇ 10 ⁇ 2 g/ ml.
  • the reductant is one or more selected from the group consisting of hydrazine hydrate, ascorbic acid, sodium citrate, and sodium borohydride, and the reductant is added in such an amount that the molar ratio of the reductant to the metal ions is in the range of 3.6:1 to 18:1.
  • the reaction time of step S 01 is preferably in the range of 10 to 45 min, in order to save energy.
  • the surface treating agent is polyvinylpyrrolidone
  • the solvent is water
  • the concentration of the surface treating agent is in the range of 0.005 to 0.1 g/ml.
  • the precipitating agent in step S 03 is ammonium carbonate, and the ammonium carbonate is in excess of 25% in the amount of substance in the solution of step S 03 . Thereby the precipitate is ensured to proceed completely. Following the ammonium carbonate is added in step S 03 , a white precipitate will form, after the mixture is stirred for a certain time and finished the reaction, the precipitate is dried in the oven to obtain the precursor.
  • the heat treatment in step S04 is that the precursor being placed in a muffle furnace at 600° C. to 1000° C. for 2 to 10 hours.
  • the reduction treatment is that the heat treated precursor being reduced at 1300° C. to 1600° C. for 1 to 8 hours in a reducing atmosphere, and the reducing atmosphere is one or more selected from the group consisting of a mixed gas of nitrogen and hydrogen, carbon monoxide, and pure hydrogen.
  • the core-shell structure of the luminescent material is formed by coating metal particles, which improves the internal quantum efficiency of the luminescent material, and the addition of metal nano-particles enhances its luminous intensity, furthermore the luminescent material has good stability, and has a spherical profile, and the size, profile thereof are controllable, the spherical profile has a higher bulk density, which facilitates the process of coating screen and improves the display effect of the coated screen; additionally, the present method employs the process of precipitation, which lowers the temperature of the synthesis reaction, and the process for preparation is simple, low equipment requirements, pollution-free, easy to control, thus has broad prospects for production applications.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Luminescent Compositions (AREA)
US13/812,908 2010-07-30 2010-07-30 Metal nano particles doped with silicate luminescent materials and preparation methods thereof Expired - Fee Related US9206353B2 (en)

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PCT/CN2010/075577 WO2012012947A1 (zh) 2010-07-30 2010-07-30 掺杂金属纳米粒子的硅酸盐发光材料及其制备方法

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EP2832820B1 (en) * 2012-05-08 2016-08-03 Ocean's King Lighting Science&Technology Co., Ltd. Titanate luminescent material and preparation method therefor
JP2015531413A (ja) * 2012-09-11 2015-11-02 オーシャンズ キング ライティング サイエンス アンド テクノロジー シーオー．，エルティーディー ケイ酸塩発光材料、及び、その製造方法
KR101983027B1 (ko) * 2013-01-31 2019-05-28 서울대학교산학협력단 수분산성이 뛰어난 실리카 나노입자 제조 방법
CN104119892A (zh) * 2013-04-26 2014-10-29 海洋王照明科技股份有限公司 一种包覆金属纳米粒子的硅酸盐发光材料及其制备方法
EP3300128B1 (en) * 2016-09-21 2021-03-03 Vestel Elektronik Sanayi ve Ticaret A.S. Phosphor arrangement and method

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US20060261309A1 (en) * 2004-08-04 2006-11-23 Intematix Corporation Two-phase silicate-based yellow phosphor

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JP5118837B2 (ja) * 2005-10-25 2013-01-16 インテマティックス・コーポレーション シリケート系オレンジ色蛍光体
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Publication number Priority date Publication date Assignee Title
US20050264161A1 (en) * 2004-05-27 2005-12-01 Hitoshi Oaku Light emitting device
US20060261309A1 (en) * 2004-08-04 2006-11-23 Intematix Corporation Two-phase silicate-based yellow phosphor

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EP2599852A4 (en) 2014-12-24
EP2599852A1 (en) 2013-06-05
US20130126785A1 (en) 2013-05-23
CN103025847B (zh) 2014-08-13
JP2013532743A (ja) 2013-08-19
WO2012012947A1 (zh) 2012-02-02
EP2599852B1 (en) 2016-03-02
CN103025847A (zh) 2013-04-03
JP5570663B2 (ja) 2014-08-13

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